Hair treatment comprising acrylic/silicone copolymer and cosmetic hair preparation containing the treatment

ABSTRACT

A hair treatment agent comprising an acryl/silicone copolymer (A) having at least one hydrolyzable silyl group per molecule and a hair cosmetic comprising the treatment agent are provided. The hair treatment agent and cosmetic comprising the same maintain good conditioning effect for a prolonged period of time.

FIELD OF THE TECHNOLOGY

This invention relates to an organopolysiloxane hair treatment agent anda hair cosmetic comprising the treatment agent. The hair treatment agentincreases effects of applying hair rinse, hair conditioner or hairtreatment product to the hair and improves durability of the effects.

BACKGROUND OF THE INVENTION

Nowadays people wash hair everyday and casually perm or color. Hairdamages physically or chemically caused by the hair wash, perm or colorare serious problems. For damaged hair, conditioning is necessary. As aconditioning agent, oils, cationic surfactants, proteins andhydrolysates thereof, moisturizer, higher alcohols, and emulsions areused. However, conditioning effects of the oils, cationic surfactants,proteins and hydrolysates thereof, moisturizer, higher alcohols, andemulsions are lost by a hair wash and not durable.

A hair treatment agent has been strongly desired which resists hair washto maintain effects of the conditioning. As a method to maintainconditioning effects, Japanese Patent Application Laid-Open No.2001-226236 discloses a method to treat the hair with amethylhydrogenpolysiloxane. The treatment with the polysiloxane isindeed effective but not sufficient. Moreover, unreacted Si—H bondsremain after the treatment, which sometimes cause generation of hydrogengas. Thus, a hair treatment agent is desired which maintains hairconditioning effect.

DISCLOSURE OF THE INVENTION

As a result of intensive studies, the present inventors have found thatthe aforesaid problem of the conventional treatment agents are solved,that is, conditioning effect is improved and retained, by using anacryl/silicone copolymer hair treatment agent and a hair cosmeticcomprising the treatment agent.

Thus, the present provides a hair treatment agent comprising anacryl/silicone copolymer (A) having at least one hydrolyzable silylgroup per molecule and a hair cosmetic comprising the hair treatmentagent. Preferably, the hydrolyzable silyl group is—Si(CH₃)_(3-m)(OR)_(m).

The present invention also provides a two-agent hair cosmetic kitcomposed of a first agent comprising at least one selected from thegroup consisting of amino-modified silicones, amino acid-modifiedsilicones, and carboxyl-modified silicones, and a second agentcomprising the aforesaid hair treatment agent, and a three-agent haircosmetic kit composed of the aforesaid hair cosmetic kit and anamino-modified silicone.

The aforesaid cosmetic may further comprise at least one selected froman unctuous agent, water, a compound having an alcoholic hydroxyl group,a water-soluble or water-swelling polymer, a surfactant, resins such asa crosslinked organopolysiloxane, and powder and/or coloring agent.

The aforesaid cosmetic is in the form of liquid, milky lotion, cream,solid, paste, gel, multilayer, mousse, spray or stick.

PREFERRED EMBODIMENTS OF THE INVENTION

A hair treatment agent of the present invention comprises anacryl/silicone copolymer having at least one hydrolyzable silyl groupper molecule. The acryl/silicone copolymer may be of any type such as ablock copolymer or a graft copolymer as long as it has at least onehydrolyzable silyl group per molecule. Preferably, the acryl/siliconecopolymer is an acryl/silicone graft copolymer having an acrylic polymerbackbone and an organopolysiloxane polymer branch.

Preferred hydrolyzable silyl group has a —Si—O— moiety, for example, analkoxysilyl group or acetoxysilyl group. More preferred silyl group isrepresented by the formula, —Si (CH₃)_(3-m)(OR)_(m), wherein R is analkyl, alicyclic, alkenyl, aryl, or aralkyl group, preferably an alkylor alkenyl group having 1 to 4 carbon atoms. Most preferably, R is anethyl group. In the above formula, m is an integer of from 1 to 3. Whenm is 2 or 3, a plurality of R's may be different from each other.Example of preferred hydrolyzable silyl group includedimethylethoxysilyl group, methyldiethoxysilyl group and triethoxysilylgroup, among which triethoxysilyl group is particularly preferred.

Preferably, the acryl/silicone copolymer has the following repeatingunits of (1), (2) and (3).

In the repeating units of from (1) to (3), R1, R² and R³ may be the samewith or different from each other and are selected from the groupconsisting of alkyl groups having 1 to 30 carbon atoms, aryl groups,aralkyl groups and fluorinated alkyl groups,

R⁴ and R⁶ may be the same with or different from each other and areselected from the group consisting of a hydrogen atom and a methylgroup,

R⁵ may be the same with or different from each other and is analkyleneoxycarbonyl group having 2 to 11 carbon atoms or a phenylenegroup,

R⁷ is an alkyl group having 1 to 30 carbon atoms,

X is the hydrolyzable silyl group as described above, and

n is an integer of from 3 to 500.

The acryl/silicone graft copolymer can be prepared by reacting anacrylic polymer with an organopolysiloxane. Preferably, for the reasonof easiness in production and molecular design, so-called macromonomermethod is employed by copolymerizing an organopolysiloxane representedby the following formula (4) having a radically polymerizable group, anacrylic monomer represented by the following formula (5), and a silanecompound represented by the following formula (6) having a radicallypolymerizable group,

-   -   wherein R¹, R² and R³ may be the same with or different from        each other and are selected from the group consisting of alkyl        groups having 1 to 30 carbon atoms, aryl groups, aralkyl groups        and fluorinated alkyl groups, A is a radically polymerizable        group represented by the following formula (7),        CH₂═C(R⁴)R⁵—  (7),    -   wherein R⁴ is a hydrogen atom or a methyl group and R⁵ is an        alkyleneoxycarbonyl group having 2 to 11 carbon atoms or a        phenylene group, and

n is an integer of from 3 to 500;CH₂═C(R⁶)COOR⁷  (5),

wherein R⁶ is a hydrogen atom or a methyl group and R⁷ is an alkyl grouphaving 1 to 30 carbon atoms;B—Si(CH₃)_(3-m)(OR⁸)_(m)  (6),

wherein B is selected from the groups defined for A above, independentlyof A, R⁸ is an alkyl group having 1 to 4 carbon atoms or an alkenylgroup, m is an integer of from 1 to 3, and R⁸'s may be different fromeach other when m is 2 or 3.

The organopolysiloxane compound represented by the formula (6) having aradically polymerizable group is called a silicone macromonomer. It hasthe radically polymerizable group at one end only. From the compound,the repeating unit (1) can be derived. In the formula (4), A representsa monovalent organic group having a radically polymerizable group and isrepresented by the formula (7) described above. Examples of A include(meth)acryloxymethyl group, (meth)acryloxypropyl group,(meth)acryloxydecyl group, styryl group, and α-methylstyryl group, amongwhich a (meth)acryloxypropyl group is preferred.

In the formulae (1) and (4), examples of R¹ include alkyl groups such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyland cyclohexyl groups; aryl groups such as phenyl and tolyl groups;aralkyl groups such as benzyl and phenetyl groups; and fluorinated alkylgroups such as trifluoropropyl and nonafluorobutylethyl groups.Preferably, most of R¹ are methyl groups because of good feel to thetouch.

In the formulae (1) and (4), n is an integer of from 3 to 500,preferably from 9 to 200. An acryl/silicone copolymer with n less thanthe aforesaid lower limit may not provide satisfactory conditioningeffect. An organopolysiloxane compound with n above the aforesaid upperlimit may not copolymerize with the acrylic monomer or the radicallypolymerizable silane compound with ease to make it difficult to obtain adesired copolymer.

From the acrylic monomer of the formula (5), the repeating unit (2) canbe derived. Examples of the monomer include methyl(meth)acrylate,ethyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate,tert-butyl(meth)acrylate, cyclohexyl(meth)acrylate,2-ethylhexyl(meth)acrylate, tridecyl(meth)acrylate,stearyl(meth)acrylate, isostearyl(meth)acrylate, behenyl(meth)acrylate,and a combination thereof. Preferably, methyl(meth)acrylate or acombination of any one of the aforesaid monomers which monomer can givea homopolymer having a higher glass transition temperature (Tg), andanother monomer of the aforesaid monomers which gives a homopolymerhaving a low Tg.

From the radically polymerizable silane compound of the formula (6), theaforesaid repeating unit (3) can be derived. Examples of the silanecompound include γ-methacryloxypropyl-trimethoxysilane,γ-methacryloxypropyl-methyldimethoxysilane,γ-methacryloxypropyl-dimethylmethoxysilane,γ-methacryloxypropyl-triethoxysilane,γ-methacryloxypropyl-methyldiethoxysilane,γ-methacryloxypropyl-tributhoxysilane,γ-methacryloxypropyl-isopropenoxysilane,γ-acryloxypropyl-trimethoxysilane, γ-acryloxymethyl-trimethoxysilane,γ-acryloxypropyl-triethoxysilane, γ-acryloxypropylmethyl-diethoxysilane,styryltrimethoxysilane, styryltriethoxysilane,α-methylstyryltrimethoxysilane, and a mixture thereof. Preferably,γ-methacryloxypropyl-triethoxysilane is used.

A ratio of the monomers of the formulas (4), (5) and (6) is such thatthe organopolysiloxane compound of the formula (4) having a radicallypolymerizable group is in an amount of from 1 to 97 wt %, preferablyfrom 5 to 90 wt %, the acrylic monomer of the formula (5) is in anamount of from 0 to 95 wt %, preferably from 2 to 60 wt %, and theradically polymerizable silane compound of the formula (6) is in anamount of from 1 to 10 wt %, preferably from 2 to 7 wt %, based on atotal weight of the monomers. If the organopolysiloxane compound of theformula (4) is used less than the aforesaid lower limit, satisfactoryeffect by hair treating may not be obtained. More amount than theaforesaid upper limit of the organopolysiloxane compound may give acopolymer which does not adsorb on or react with the hairsatisfactorily. If the acrylic monomer of the formula (5) is used morethan the aforesaid upper limit, a copolymer having enough resistance towater may not be obtained. A less amount of the radically polymerizablesilane compound of the formula (6) than the aforesaid lower limit maynot give a copolymer having satisfactory reactivity with the hair. Moreamount than the aforesaid upper limit of the silane may give a copolymerwhich react among themselves in addition to with the hair. Taking theaforesaid matters into consideration, the ratio can be determined.

In addition to the aforesaid monomers, other radically polymerizablecompound in an amount not to adversely affect the present invention canbe copolymerized. Examples of the other radically copolymerizablemonomer include carboxylic acids such as (meth)acrylic acid, fumaricacid and maleic acid; hydroxyalkyl esters such ashydroxyethyl(meth)acrylate and hydroxypropyl(meth)acrylate; acidicamides such as (meth)acrylamide; fluorinated alkyl esters such asperfluorooctylethyl(meth)acrylate, perfluorobutylethyl(meth)acrylate,styrene, acrylonitrile, vinyl acetate, vinyl pyrrolidone,polyoxyethylene mono(meth)acrylate, polyoxypropylene mono(meth)acrylate,polyoxy(ethylene/propylene) mono(meth)acrylate, polycaprolactonemono(meth)acrylate, tris(trimethylsiloxy)silylpropyl methacrylate, andtris(trimethylsiloxy)silyl styrene.

Any method of copolymerisation can be used, for example, solutionpolymerization, emulsion polymerization, suspension polymerization, ormass polymerization, among which solution polymerization is preferredbecause of uniformity of a resulting polymer and easiness in molecularweight control. As a solvent for the solution polymerization, the one inwhich the aforesaid monomers and a polymer obtained can be uniformlydissolved. Examples of the solvent include toluene, xylene, ethanol,isopropanol, n-butanol, acetone, methyl ethyl ketone, methyl isobutylketone, ethyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether,and tetrahydrofuran.

As a polymerization initiator, any conventionally used radical initiatormay be used. Examples of the initiator include organic peroxides such asbenzoylperoxide and dicumyl peroxide; and azo compounds such asazobisisobutylonitrile. A mercaptan derivative as a chain transfer agentmay be used to control molecular weight of a polymer, for example,dodecyl mercaptan and mercaptopropyl trimethoxysilane. Use of a compoundhaving a hydrolyzable group as aforementioned mercaptopropyltrimethoxysilane has an advantage that it adds a hydrolyzable silylgroup to a polymer terminal. A solution of a resulting polymer can beused as such or may be diluted. Alternatively, the polymer is isolatedor re-dissolved in another solvent for use as a hair treatment agent.

Preferably, the acryl/silicone copolymer obtained has a molecularweight, determined by GPC, of from 5,000 to 200,000, more preferablyfrom 10,000 to 100,000. An acrylic-silicone copolymer having a lowermolecular weight than the aforesaid lower limit may not showsatisfactory effect in treating the hair. An acrylic-silicone copolymerhaving a higher molecular weight than the aforesaid upper limit may notgive a hair cosmetic having a good usability.

In the present invention, the organopolysiloxane hair treatment agent(A) can be used in various ways. It can be used alone in the from of adispersion or a solution in an organic solvent which is applied directlyon the hair; it can be used in a two-agent kit composed of an aqueous ornon-aqueous first agent selected from the group consisting ofamino-modified silicone, amino acid-modified silicone andcarboxyl-modified silicone, and the present hair treatment agent (A) asa second agent; and it can be used in a three-agent kit composed of afirst agent comprising an aqueous or non-aqueous amino-modifiedsilicone, a second agent comprising the present hair treatment agent(A), and a third agent comprising an aqueous or non-aqueousamino-modified silicone.

Preferably, an amino-modified silicone is used as the first agent andthe present hair treatment agent is used as the non-aqueous secondagent. Alternatively, an amino-modified silicone is used as the firstagent, the present hair treatment agent is used as the non-aqueoussecond agent, and an aqueous or non-aqueous amino-modified silicone isused as the third agent. In both the two-agent and the three-agent kits,it was found that conditioning effect is maintained well by asynergistic effect of the amino-modified silicone and the present hairtreatment agent.

Examples of the amino-modified silicone include those having aminogroups grafted to a silicone backbone, those having an amino groupbonded to either one end of a silicone backbone, those having aminogroups bonded to both ends of a silicone backbone, those having aminogroups at both ends of a silicone backbone and an amino group grafted tothe silicone backbone, and those having a silicone side chain and anamino group both grafted to a silicone backbone. Preferably, theamino-modified silicone represented by the following formula is used.

In the formula (8), A is —R¹⁰NH₂ or —R¹⁰NHR¹¹NH₂, wherein R¹⁰ and R¹¹are alkylene groups having 1 to 8 carbon atoms,

R⁹ may be the same with or different from each other and is selectedfrom the group consisting of alkyl groups having 1 to 30 carbon atoms,alicyclic groups, aryl groups, aralkyl groups, and fluorinated alkylgroups,

m and n may be the same with and different from each other and areintegers of from 0 to 300, and s and t may be the same with or differentfrom each other and are integers of from 0 to 3 with 1≦n+s+t.

Examples of R⁹ include alkyl group such as methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; alicyclic groupssuch as cyclopentyl and cyclohexyl groups; aryl groups such as phenyland tolyl groups; aralkyl groups such as benzyl and phenetyl groups; andfluorinated alkyl groups such as trifluoropropyl andheptadecafluorodecyl groups, among which methyl, phenyl, andtrifluoropropyl groups are preferred.

Examples of R¹⁰ and R¹¹ include methylene, ethylene, propylene,butylene, and pentylene groups, among which methylene, ethylene andpropylene groups are preferred.

The present hair cosmetic may comprise various components contained inconventional cosmetics. Those components may be contained not only inone agent system composed of the component (A), but also in two- orthree-agent kit as a whole, that is, the components may be incorporatedin one or more of the agents from first to third one. These componentswill be explained below.

The present cosmetic may further comprise one or more of unctuous agent(B). Any conventional unctuous agents can be used whether they are inthe form of solid, semisolid or liquid. Examples of the unctuous agentsinclude natural animal or plant oils, semi-synthetic oils, hydrocarbonoils, higher alcohol oils, ester oils and conventional silicone oils.

Examples of the natural animal or plant oils and semi-synthetic oilsinclude avocado oil, linseed oil, almond oil, Chinese wax, perilla oil,olive oil, cacao butter, kapok wax, kaya oil, carnauba wax, liver oil,candellila wax, beef tallow, beef foot oil, beef bone fat, hydrogenatedbeef tallow, apricot kernel oil, spermaceti, hydrogenated oil, wheatgerm oil, sesame oil, rice germ oil, rice branoil, sugarcane wax,sasanquaoil, safflower oil, shea butter, Chinese tung oil, cinnamon oil,jojoba wax, shellac wax, turtle oil, soybean oil, tea seed oil, tsubakioil, evening primrose oil, corn oil, lard, rape seed oil, Japanese tungoil, rice-bran wax, germ oil, horse fat, persic oil, palm oil, palmkernel oil, castor oil, hydrogenated castor oil, caster oil fatty acidmethyl ester, sunflower oil, grape seed oil, bayberry wax, jojoba oil,macadamia nut oil, beeds wax, mink oil, cottonseed oil, cotton wax,Japan wax, haze kernel oil, montan wax, coconut oil, hydrogenatedcoconut oil, tricoconut oil fatty acid glyceride, mutton-tallow, peanutoil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hardlanolin, lanolin acetate, lanolin fatty acid isopropyl, hexyl laurate,POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fattyacid polyethylene glycol, POE hydrogenated lanolin alcohol ether, andegg yolk oil, wherein the term “POE” stands for polyoxyethylene.

Examples of the hydrocarbon oil include ozokerite, squalane, squalene,ceresine, paraffin, paraffin wax, liquid paraffin, pristane,polyisobutylene, microcrystalline wax and Vaseline; and those of ahigher fatty acid which can be mixed include lauric acid, myristic acid,palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid,linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid(EPA), docosahexaenoic acid (DHA), isostearic acid and 12-hydroxystearicacid.

Examples of the higher alcohol include lauryl alcohol, myristyl alcohol,palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol,oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol,cetostearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol, POEcholesterol ether, monostearyl glycerin ether (batyl alcohol) andmonooleyl glyceryl ether (cerakyl alcohol).

Examples of the ester oil include diisobutyl adipate, 2-hexyldecyladipate, di-2-heptylundecyl adipate, N-alkylglycol monoisostearates,isocetyl isostearate, trimethylolpropane triisostearic acid ester,ethylene glycol di-2-ethylhexanoic acid ester, cetyl 2-ethylhexanoate,trimethylolpropane tri-2-ethylhexanoic acid ester, pentaerythritoltetra-2-ethylhexanoic acid ester, cetyl octanoate, octyldodecyl gumester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycoldicapric acid ester, triethyl citrate, 2-ethylhexyl cinnamate, amylacetate, ethyl acetate, butyl acetate, isocetyl stearate, butylstearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate,myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate,2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl12-hydroxystearate, dipentaerythritol fatty acid esters, isopropylmyristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristylmyristate, hexyldecyl dimethylocanoate, ethyl laurate, hexyl laurate,N-lauroyl-L-glutaminic acid 2-octyldodecyl ester and diisostearyl malicacid; and examples of glyceride oil which can be mixed therein includeacetoglyceride, triisooctanoic acid glycride, triisostearic acidglyceride, triisopalmitic acid glyceride, tri-2-ethylhexanoic acidglyceride, monostearic acid glyceride, di-2-heptylundecanoic acidglyceride, trimyristic acid glyceride and myristic acid isostearic aciddiglyceride.

Examples of the conventional silicone oil include organopolysiloxaneshaving a viscosity of from a low value to a high value, preferably from0.65 to 1,000,000 mm²/s, such as dimethylpolysiloxane,methylphenylpolysiloxane, methylhydrogenpolysiloxane and a copolymer ofdimethylsiloxane and methylphenylsiloxane; cyclic siloxanes, such asoctamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane,tetramethyl-tetrahydrogencyclotetrasiloxane; silicone rubbers, such asgummy dimethylpolysiloxanes having high polymerization degrees and gummydimethylsiloxane-methylphenylsiloxane copolymers having highpolymerization degrees; and cyclosiloxane solutions of silicone rubber,trimethylsiloxysilicate, cyclosiloxane solutions oftrimethylsiloxysilicate, higher alkoxy-modified silicones such asstearoxysilicone, higher fatty acid-modified silicones, alkyl-modifiedsilicones, siliconols, fluorine-modified silicones, and solutions ofsilicone resins in a cyclic siloxane.

Examples of fluorine-containing oil include perfluoropolyether,perfluorodecalin and perfluorooctane.

A content of these unctuous agents (B) may vary depending on the form ofthe cosmetic and range from 0.01 to 99 wt % based on a total weight ofthe cosmetic.

The present hair cosmetic may further comprise (C) water according to apurpose of the cosmetic. A content of water (C) may vary depending onthe form of the cosmetic and ranges from 0.01 to 99 wt % based on atotal weight of the cosmetic.

The present cosmetic may further comprise one or more of a compound (D)having at least one alcoholic hydroxyl group per molecule, depending ona purposes of the cosmetic. Examples of the compoud (D) include loweralcohols, such as ethanol and isopropanol; sugar alcohols, such assorbitol and maltose; sterols, such as cholesterol, sitosterol,phytosterol and lanosterol; and polyhydric alcohols such as butyleneglycols, propylene glycols, dibutylene glycols, and pentylene glycols.The compound (D) may be incorporated in the cosmetic in an amount offrom 0.1 to 98 wt % based on a total weight of the cosmetic.

The present cosmetic may further comprise one or more of a water-solubleor water-swellig polymer (E). Examples of the water-soluble orwater-swellig polymer include plant origin polymers, such as gum arabic,tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan,pectin, agar, quince seed, starch (rice, corn, potato, wheat), algecolloid, tranto gum and locust bean gum; microbial polymers, such asxanthan gum, dextran, succinoglucan and pullulan; animal polymers, suchas collagen, casein, albumin and gelatin; starch polymers, such ascarboxymethyl starch and methylhydroxypropyl starch; cellulose polymers,such as methyl cellulose, ethyl cellulose, methylhydroxypropylcellulose, carboxymethyl cellulose, hydroxymethyl cellulose,hydroxypropyl cellulose, nitrocellulose, sodium cellulose sulfate,sodium carboxymethylcellulose, crystalline cellulose and powderycellulose; alginic acid polymers, such as sodium alginate and propyleneglycol ester of alginic acid; vinyl polymers, such as polyvinyl methylether and carboxyvinyl polymer; polyoxyethylene polymers;polyoxyethylene-polyoxypropylene copolymers; acrylic polymers, such assodium polyacrylate, polyethylacrylate and polyacrylamide; othersynthetic water-soluble polymers, such as polyethyleneimines andcationic polymers; and inorganic water-soluble polymers, such asbentonite, aluminum magnesium silicate, montmorillonite, beidellite,nontronite, saponite, hectorite and silicic acid anhydride. Thewater-soluble polymer encompasses film-forming agents, such as polyvinylalcohol and polyvinyl pyrrolidine, are also included. It may beincorporated in the cosmetic in an amount of from 0.1 to 25 wt % basedon a total weight of the cosmetic.

The present hair cosmetic may further comprise one or more of asurfactant (F) according to a purpose of the cosmetic. Examples of thesurfactant include anionic, cationic, nonionic and amphotericsurfactants and are not limited to a particuar one. Any surfactant canbe used so long as it is used in ordinary cosmetics.

Examples of the anionic surfactant include fatty acid soap, such assodium stearate or triethanolamine palmitate; alkyl ether carboxylicacids and salts thereof; salts of amino acid-fatty acid condensates;alkanesulfonates; alkenesulfonates; sulfonated fatty acid esters;sulfonated fatty acid amides; sulfonates of formaldehyde condensatetype; alkylsulfates; higher secondary alcohol sulfates; alkyl and arylether sulfates; fatty acid ether sulfates, fatty acid alkylolamidesulfates; ether sulfates, such as Turkeky red oil; alkyl phosphates;ether phosphates; alkyl aryl ether phosphates; amide phosphates; andactive agents of N-acylamino acid type.

Examples of the cationic surfactant include amine salts, such asalkylamie salts, polyamines and aminoalcohol fatty acid derivatives,quaternary alkylammonium salts, quaternary arylammonium salts,pyridinium salts and imidazolium salts.

Examples of the nonionic surfactant include sorbitan fatty acid esters,glycerin fatty acid esters, polyglycerin fatty acid esters, propyleneglycol fatty acid esters, polyethylene glycol fatty acid esters, sucrosefatty acid esters, polyoxyethylene alkyl ethers, polyoxypropylene alkylethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acidesters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylenesorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters,polyoxyethylene propylene glycol fatty acid esters, polyoxyethylenecastor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylenephytostanol ehter, polyoxyethylene phytosterol ether, polyoxyethylenecholestanol ether, polyoxyethylene cholesteryl ether, linear or branchedpolyoxyalkylene-modified organopolysiloxanes, linear or branchedorganopolysiloxanes modified with both polyoxyalkylene and alkyl groups,linear or branched polyglycerin-modified organopolysiloxanes,alkanolamides, sugar ethers and sugar amides; and examples of a usableamphoteric surfactant include betaine, aminocarboxylates and imdazolinederivatives. The surfactant may be incorporated in the cosmeticpreferably in an amount of from 0.1 to 20 wt %, particularly 0.2 to 10wt %, based on a total weight of the cosmetic.

The present cosmetic may further comprise one or more of a crosslinkedorganopolysiloxane (G), depending on a purpose of the cosmetic. Thecrosslinked organopolysiloxane preferably has been swelled with asilicone having a low viscosity of from 0.65 to 10.0 mm²/sec (25° C.) inan amount larger than a weight of the organopolysiloxane (G). Preferedcrosslinked organopolysiloxane is a reaction product of anorganopolysiloxane having at least two alkenyl groups per molecule andan organohydrogenpolysiloxane having a Si—H bond. The crosslinkedorganopolysiloxane may have at least one moiety selected frompolyoxyalkylene, polygrycerol, alkyl, alkenyl, aryl and fluoroalkylmoieties. The crosslinked organopolysiloxanes may be incorporated in thecosmetic preferably in an amount of from 0.1 to 50 wt %, more preferablyfrom 1 to 30 wt %, based on a total weight of the cosmetic.

The present cosmetic may further comprise one or more of a conventionalsilicone resin (H). Preferred silicone resin is an acryl/silicone graftor block copolymer without having a hydrolyzable silyl group. Use may bemade of an acryl/silicone resin having no hydrolysable silyl group andat least one moiety selected from the group consisting of pyrrolidonemoieties, long-chain alkyl moieties, polyoxyalkylene moieties,fluoroalkyl moieties and carboxylic acid moieties.

Preferably, this silicone resin is a silicone compound having a networkstructure represented as MQ, MDQ, MT, MDT, or MDTQ. Use may be made of asilicone network compound having at least one moiety selected from thegroup consisting of pyrrolidone, long-chain alkyl, polyoxyalkylene,fluoroalkyl, and amino moieties.

The silicone resin may be incorporated in the cosmetic preferably in anamount of from 0.1 to 20 wt %, more preferably from 1 to 10 wt %.

The present cosmetic may further comprise one or more of powder and/orcoloring agent (I) depending on a purpose of the cosmetic. Any powderconventionally used in cosmetics can be used irrespective of its form,for example, spherical, acicular or tabular; its size, for example, fumestate, fine grain or pigment grade; and its structure, for example,porous or nonporous. Examples include inorganic powder, organic powder,metal salt surfactant powder, colored pigments, pearl pigments, metallicpowder pigments and natural pigments.

Examples of the inorganic powder include titanium dioxide, zirconiumoxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate,calcium sulfate, magnesium sulfate, calcium carbonate, magnesiumcarbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica,phlogopite, ruby mica, biotite, lipidolite, silicic acid, silicic acidanhydride, aluminum silicate, magnesium silicate, aluminum magnesiumsilicate, calcium silicate, barium silicate, strontium silicate, metalsalts of tungstic acid, hydroxyapatite, vermiculite, haidilite,bentonite, montmorillonite, hectorite, zeolite, ceramics powder, calciumsecondary phosphate, alumina, aluminum hydroxie, boron nitride andsilica.

Examples of the organic powder include polyamide powder, polyesterpowder, polyethylene powder, polypropylene powder, polystyrene powder,polyurethane powder, benzoguanamine powder, polymethylbenzoguanaminepowder, polytetrafluoroethylene powder, polymethylmethacrylate powder,cellulose powder, silk powder, nylon powder such as 12-nylon powder or6-nylon powder, crosslinked dimethylsilicone fine powder,polymethylsilsesquioxane fine powder, powder of crosslinked siliconecomposite with polymethylsilsesquioxane bonded to the silicone,styrene-acrylic acid copolymer powder, divinylbenzene-styrene copolymerpowder, vinyl resin powder, urea resin powder, phenol resin powder,fluororesin powder, silicone resin powder, acrylic resin powder,melamine resin powder, epoxy resin powder, polycarbonate resin powder,microcrystalline fiber powder, starch powder and lauroyl lysine powder.

Examples of the metal salt surfactant powder (metal soap powder) includepowders of zinc stearate, aluminum stearate, calcium stearate, magnesiumstearate, zinc myristate, magensium myristate, zinc cetylphosphate,calcium cetylphosphate and zinc sodium cetylphosphate.

Examples of the colored pigment include red pigments, such as ironoxide, iron hydroxide and iron titanate; inorganic brown pigments, suchas γ-iron oxide; inorganic yellow pigments, such as iron oxide yellowand loess; inorganic black pigments, such as iron oxide black and carbonblack; inorganic violet pigments, such as manganese violet and cobaltviolet; inorganic green pigments, such as chromium hydroxide, chromiumoxide, cobalt oxide and cobalt titanate; inorganic blue pigments, suchas Prussian blue and ultramarine blue; lakes of tar pigments; lakes ofnatural dyes; and a composite powder of two or more of above.

Examples of the pearl pigment include titanium oxide-coated mica,bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titaniumoxide-coated talc, fish scales, and titanium oxide-coated colored mica.Examples of the metallic powder pigment include aluminum powder, copperpowder and stainless powder. Examples of the tar pigment include Red No.3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, RedNo. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No.230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No.202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, BlueNo. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No.204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204,Orange No. 206 and Orange No. 207; and examples of the natural pigmentinclude powders of carminic acid, laccaic acid, carthamin, bradilin andcrocin.

The powder may be used as in a composite form or may be treated with acommonly used oil, silicone oil, fluorocompound, or surfactant. Thepowder may be used as a mixture of two or more thereof, if desired. Thepowder is incorporated in the cosmetic preferably in an amount of from0.1 to 99 wt % based on a total weight of the cosmetic.

To the present cosmetic may further comprise ingredients used in generalcosmetics such as oil-soluble gelling agents, clay minerals modifiedwith organic compounds, resins, ultraviolet absorbents or scatteringmaterial, moisturizing agents, antiseptics, antimicrobial agents,perfume, salts, antioxidants, pH regulators, chelating agents,refrigerant, anti-inflammatory agents, skin beautifying components (askin whitener, a cell activator, a rough dry skin improver, a bloodcirculation promoter, a skin astringent and an anti-seborrheic agent),vitamins, amino acids, nucleic acids, hormones and clathrate compounds,and polymers for hair setting, in an amount not to have adverseinfluences on the effects of the present invention.

Examples of the oil-soluble gelling agent include metal soaps, such asaluminum stearate, magnesium stearate and zinc myristate; amino acidderivatives, such as N-lauroyl-L-glutamic acid and α,γ-di-n-butylamine;dextrin fatty acid esters, such as dextrin palmitic acid ester, dextrinstearic acid ester and dextrin 2-ethylhexaminic acid palmitic acidester; sucrose fatty acid esters, such as sucrose palmitic acid esterand sucrose stearic acid ester; benzylidene derivatives of sorbitol,such as monobenzylidene sorbitol and dibenzylidene sorbitol; and clayminerals modified with organic compounds, such as dimethylbenzyldodecylammonium montmorillonite clay and dimethyldioctadecyl ammoniummontmorillonite clay.

Examples of the ultraviolet light absorbent include those of benzoicacid type, such as p-aminobenzoic acid; those of anthranilic acid type,such as methyl anthranilate; those of salicylic acid type, such asmethyl salicylate; those of succinic acid type, such as octylp-methoxysuccinate; those of benzophenone type, such as2,4-dihydroxybenzophenone; those of urocanic acid type, such as ethylurocanate; and those of dibenzoylmethane type, such as4-t-butyl-4′-methoxydibenzoylmethane. Examples of ultraviolet scatteringmaterial include titanium oxide fine powder, fine powder of titaniumoxide containing iron, zinc oxide fine powder, cerium oxide fine powder,a composed powder of two or more of these and powder which absorbs andscatters ultraviolet.

Examples of the moisturizing agent include glycerin, sorbitol, propyleneglycol, dipropylene glycol, 1,3-butylene glycol, glucose, xylitol,maltitol, polyethylene glycol, hyaluromic acid, chondroitin sulfuricacid, pyrrolidone carboxylic acid, polyoxyethylene glycoside, andpolyoxypropylene methylglycoside.

Examples of the antiseptic agent include alkyl p-hydroxybenzoates,benzoic acid, sodium benzoate, sorbic acid, potassium sorbate andphenoxyethanol; and those of an antimicrobial agent which can be addedinclude benzoic acid, salicylic acid, carbolic acid, sorbic acid, alkylp-hydroxybenzoates, p-chlorometacresol, hexachlorophene, benzalkoniumchloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizerand phenoxyethanol.

Examples of the antioxidant include tocopherol, butylhydroxyanisole,dibutylhydroxytoluene and phytic acid; those of a pH regulator which canbe added include lactic acid, citric acid, glycolic acid, succinic acid,tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogencarbonate and ammonium hydrogen carbonate; those of a chelating agentwhich can be added include alanine, sodium ethylenediaminetetraacetate,sodium polyphosphate, sodium metaphosphate and phosphoric acid; those ofa refrigerant which can be added include L-menthol and camphor; andthose of an anti-inflammatory agent which can added include allantoin,glycyrrhizin and salts thereof, glycyrrhetinic acid and stearylglycyrrhetinate, tranexamic acid and azulene.

Examples of the skin-beautifying component include whitening agents,such as placenta extract, arbutin, glutathione and Yukinoshita extract;cell activators, such as royal jelly, photosensitizer, cholesterolderivatives and calf blood extract; rough dry skin improvers; bloodcirculation improvers, such as nonylic acid vanillyl amide, benzylnicotinate, β-butoxyethyl nicotinate, capsaicin, zingerone, cantharistincture, ichtammol, caffeine, tannic acid, α-borneol,tocopherylnicotinate, inositol hexanicotinate, cyclandelate,cinnarizine, tolazoline, acetyl choline, verapamil, cepharanthin andγ-oryzanol; skin astringents, such as zinc oxide and tannic acid; andanti-seborrheic agents, such as sulfur and thianthol.

Examples of the vitamin include vitamin A, such as vitamin A oil,retinol, retinyl acetate and retinyl palmitate; vitamin B, includingvitamin B2 such as riboflavin, riboflavin butyrate and flavin adeninenucleotide, vitamin B6 such as pyridoxine hydrochloride, pyridoxinedioctanoate and pyridoxine tripalmitate, vitamin B12 and itsderivatives, and vitamin B15 and its derivatives; vitamin C, such asL-ascorbic acid, L-ascorbic acid dipalmitic ester, sodium (L-ascorbicacid)-2-sulfate and dipotassium L-ascorbic acid diphosphate; vitamin D,such as ergocalciferol and cholecarciferol; vitamin E, such asα-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopheryl acetate,dl-α-tocopheryl nicotinate and dl-α-tocopheryl succinate; vitamin H;vitamin P; nicotinic acids, such as nicotinic acid, benzyl nicotinateand nicotinic acid amide; pantothenic acids, such as calciumpantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether andacetylpantothenyl ethyl ether; and biotin.

Examples of the amino acid include glycine, valine, leucine, isoleucine,serine, threonine, phenylaranine, alginine, lysine, aspartic acid,aspartic acid, glutamic acid, cystine, cysteine, methionine, andtryptophan; those of a nucleic acid which can be added includedeoxyribonucleic acid; and those of hormone which can be added includeestradiol and ethenyl estradiol.

Examples of the polymer for hair setting include amphoteric, anionic,cationic, and nonionic polymers, such as polymers of polyvinylpyrrolidone type such as polyvinyl pyrrolidone, vinyl pyrrolidone/vinylacetate copolymers; acidic polymers of vinyl acetate ether type such asmethyl vinyl ether/maleic acid anhydride alkyl half ester copolymer;polymers of acidic poly vinyl acetate type such as vinylacetate/crotonic acid copolymer; acidic acrylic polymers such as(meth)acrylic acid/alkyl(meth)acrylate copolymer, (meth)acrylicacid/alkyl(meth)acrylate/alkyl acrylic amide copolymer, and amphotericacrylic polymer such as N-methacryloylethyl-N,N-dimethylammoniumalpha-N-methylcarboxybetaine/alkylmetahcrylate copolymer,hydroxypropyl(metha)acrylate/butylaminoethyl methacrylate/octyl amide ofacrylic acid copolymer. Use is also made of naturally occurring polymerssuch as cellulose or derivatives thereof, keratin, collagen andderivatives thereof.

The present hair cosmetic may be in the form of liquid, milky lotion,cream, solid, paste, gel, multilayer, mousse, spray or stick.

EXAMPLES

The present invention will be explained in detail with reference toExamples, but not limited thereto. In the following, “%” means % byweight unless otherwise specified.

Synthesis Example 1

In a glass flask provided with a stirrer, a thermometer and a refluxcondenser, 50 wt % of the radically polymerizable organopolysiloxane ofthe following formula (9), 5 wt % of methyl methacrylate, 40 wt % ofstearyl methacrylate, 5 wt % of γ-methacryloxypropyl-trimethoxysilane,toluene in the same weight as a total weight of the aforesaid monomers,and azobisisobutylonitrile in an amount of 1% by weight of a totalweight of the monomers and toluene were placed and subjected topolymerization by heating under nitrogen stream at 100° C. for 10 hours.Then, toluene was distilled off at a reduced pressure. An acryl/siliconegraft copolymer for the hair thus obtained was light yellow solid havinga melting point of 30° C. and a weight average molecular weight,determined by GPC, of 42,000 in polystyrene equivalent.

Synthesis Example 2

An acryl/silicone graft copolymer was prepared as in Example 1 bycopolymerizing 50 wt % of the radically polymerizable organopolysiloxaneof the above formula (9), 30 wt % of methyl methacrylate, 7.5 wt % ofbutyl methacrylate, 7.5 wt % of 2-ethyl hexyl acrylate and 5 wt % ofγ-methacryloxypropyl-triethoxysilane. The copolymer obtained wastransparent light yellow resin having a softening point of 93° C. and aweight average molecular weight, determined by GPC, of 55,000 inpolystyrene equivalent.

Synthesis Example 3

An acryl/silicone graft copolymer was prepared as in Example 1 bycopolymerizing 90 wt % of the radically polymerizable organopolysiloxaneof the following formula (10), 50 wt % of methyl methacrylate, and 5 wt% of γ-methacryloxypropyl-triethoxysilane. The copolymer for the hairobtained was colorless transparent liquid having a viscosity at 25° C.of 270 mm²/sec, a specific gravity of 0.981, a refractive index of1.4152 and a weight average molecular weight, determined by GPC, of11,000 in polystyrene equivalent.

Example 1 Hair Spray (One-Agent Type)

Components wt % 1. Synthesis Example 2 5.0 2. Ethanol 95.0

The components described above were mixed. The mixture was packed in aspray container to prepare a hair spray. The hair spray obtained wastested by five female panelists and rated according to the followingcriteria by comparing the hair to which the hair spray was applied withthe reference hair which was not applied with the hair spray in terms ofeasiness to comb, moisturized feel, softness, and gloss. Moisturizedfeel, Mark Easiness to comb softness, and gloss 5 Much easierSignificant 4 A little easier A little more than the reference level 3Reference level Reference level 2 A little difficult A little less thanthan the reference the reference level 1 Much difficult None

The marks were averaged and used for evaluation according to thecriteria shown below.

Evaluation according to an averaged mark: Averaged mark 4.5 or higher A3.5 to below 4.5 B 2.5 to below 3.5 C 1.5 to below 2.5 D below 1.5 E

Comparative Example 1

A hair spray was prepared as in Example 1 except that amethylhydrogenpolysiloxane was used in place of the organopolysiloxaneprepared in Synthetic Example 2.

Results of Example 1 and Comparative Example 1 are as shown in Table 1below. TABLE 1 Comparative Example 1 Example 1 Easiness to comb A AMoisturized feel A B Softness A A Gloss A B

As is evident from Table 1, the hair treated with the hair spray of thepresent invention was easy to comb, moisturized, soft and glossycompared with the hair treated with methylhydrogenpolysiloxane.

Examples 2-5, Comparative Examples 2-4

Hair treatment agents each having the formulation shown in Table 2 wereprepared. TABLE 2 Ex*³. 2 Ex. 3 Ex. 4 Ex. 5 Comp. Ex. *⁴ 2 Comp. Ex. 3Comp. Ex. 4 First agent 1 Amino-modified 5 5 5 — 5 5 5 silicone*¹ 2Cetanol 8 8 8 — 8 8 8 3 Stearyl 3.5 3.5 3.5 — 3.5 3.5 3.5 trimethylammonium chloride 4 Glycerin 5 5 5 — 5 5 5 5 Purified water 78.5 78.578.5 — 78.5 78.5 78.5 Second agent 1 Synthesis 6 — —  6 — — — example 12 Synthesis — 6 — — — — — example 3 3 Synthesis — — 6 — — — — example 44 Methylhydrogen — — — — 6 6 — polysiloxane 5 Ethanol 94 94 94 94 94 94100 Third agent 1 Amino-modified — — 2 — — 2 — silicone*¹ 2 Highly — — 5— — 5 — polymerized methylpoly- siloxane solution*² 3 Cetanol — — 8 — —8 — 4 Stearyl — — 3.5 — — 3.5 — trimethyl ammonium chloride 5 Glycerin —— 3 — — 3 — 6 Purified water — — 78.5 — — 78.5 100*¹Amino-modified silicone: KF-8005, ex Shin-Etsu Chemical Co., Ltd.*²Solution of a Highly polymerized methylpolysiloxane: KF-9013, exShin-Etsu Chemical Co., Ltd.*³“Ex.” stands for Example.*⁴“Comp. Ex.” stands for Comparative Example.

Each hair treatment agent was evaluated using hair bundles for testing.

The hair bundle for testing was a bundle of ordinary hair with a lengthof 20 cm and a total weight of 6.0 g which had been shampooed andbreached with a breaching agent.

In Examples 2 and 3, the hair bundle was coated with one gram of a firstagent followed by washing with water, and then coated with one gram of asecond agent followed by drying; in Example 4, the hair bundle wastreated with a first agent and then a second agent as described above,and then coated with one gram of a third agent; and in Example 5, thehair bundle was washed and then coated with one gram of a second agent.Each of thus treated hair bundle was processed under the conventionalconditions by treating with a conventional hair treatment product,rinsing and drying.

Subsequently, the process consisting of shampooing, hair treatment witha treatment product and drying was repeated 20 times consecutively.

The hair bundles immediately after treated with the present hairtreatment agent and those after 20 cycles of the processing werecompared with as ordinary hair being a reference in easiness to comb,moisturized feel, softness, and gloss. Results are as shown in thefollowing Table. TABLE 3 Example 2 Example 3 Example 4 Example 5 Comp.Ex. 2 Comp. Ex. 3 Comp. Ex. 4 Immediately after treatment Easiness tocomb A A A A B A B Moisturized feel A A A A B B B Softeness A A A A A AB Gloss A A A A B A B After 20-cycle processing Easiness to comb A A A BD C D Moisturized feel A A A A D B D Softeness A A A A D B D Gloss A A AB D C D

As shown in Table 3, compared with the hair cosmetic of ComparativeExamples, the hair treatment cosmetics of the present invention weresuperior in all the aspects, i.e., easiness to comb, moisturizingeffect, softening effect and gloss, indicating improvement in durabilityof hair treatment applied to the hair.

In Examples 2 to 4, the hair after 20-cycle processing showed the sameresult as that of the hair immediately after treated, indicatingexcellent resistance to shampooing. Especially, Examples 2 and 5,wherein the present treatment agent is used together with theamino-modified silicone, durable coating film on the hair was formed tomaintain smoothness in combing and gloss, compared with ComparativeExample 4. Although, the effect was demonstrated by using amino-modifiedsilicones, the same effect is attained with amino acid-modifiedsilicones and carboxyl-modified silicones hair treatment agent.

1. A hair treatment composition comprising: an acryl/silicone copolymer(A) having at least one hydrolyzable silyl group per molecule; and atleast one additional ingredient suitable for application to hair, saidcomposition being in the form of liquid, milky lotion, cream, solid,paste, gel, multilayer, mousse, spray or stick.
 2. The hair treatmentcomposition according to claim 1, wherein the acryl/silicone copolymer(A) is an acryl/silicone graft copolymer having an acrylic polymerbackbone and an organopolysiloxane polymer branch.
 3. The hair treatmentcomposition according to claim 1 or 2, wherein the hydrolyzable silylgroup is—Si(CH₃)_(3-m)(OR)_(m) wherein R is an alkyl group having 1 to 10 carbonatoms, an alicyclic group, an alkenyl group, an aryl group, an aralkylgroup, or an alkaryl group, m is an integer of from 1 to 3, and R may bedifferent from each other when m is 2 or
 3. 4. The hair treatmentcomposition according to claim 1, wherein the acryl/silicone copolymer(A) has the following repeating units (1), (2) and (3):

wherein R¹, R² and R³ may be the same with or different from each otherand are selected from the group consisting of alkyl groups having 1 to30 carbon atoms, aryl groups, aralkyl groups and fluorinated alkylgroups, R⁴ and R⁶ may be the same with or different from each other andare selected from the group consisting of a hydrogen atom and a methylgroup, R⁵ may be the same with or different from each other and is analkyleneoxycarbonyl group having 2 to 11 carbon atoms or a phenylenegroup, R⁷ is an alkyl group having 1 to 30 carbon atoms, X is thehydrolyzable silyl group as described in claim 1, and n is an integer offrom 3 to
 500. 5. The hair treatment composition according to claim 1,wherein the copolymer has a weight average molecular weight of from5,000 to 200,000.
 6. A hair cosmetic comprising the hair treatmentcomposition according to claim
 1. 7. A two-component hair cosmetic kitcomposed of a first component of an ingredient which is at least oneselected from the group consisting of amino-modified silicones, aminoacid-modified silicones, and carboxyl-modified silicones, and a secondcomponent which is the hair treatment composition according to claim 1.8. A three-component hair cosmetic kit composed of the two-componenthair cosmetic kit according to claim 7 and an amino-modified silicone asthe third component.
 9. The cosmetic according to claim 7 or 8, whereinthe amino-modified silicone is at least one selected from the groupconsisting of silicones having an amino group grafted to a siliconebackbone, silicones having an amino group bonded to either one end of asilicone backbone, silicones having amino groups bonded to both ends ofa silicone backbone, silicones having amino groups bonded to both endsof a silicone backbone and an amino group grafted to the siliconebackbone, and silicones having a silicone chain and an amino group bothgrafted to a silicone backbone.
 10. The cosmetic according to claim 7,wherein the amino-modified silicone is represented by the followingformula (8),

wherein A is —R¹⁰NH₂ or —R¹⁰NHR¹¹NH₂, wherein R¹⁰ and R¹¹ are alkylenegroups having 1 to 8 carbon atoms, R⁹ may be the same with or differentfrom each other and is selected from the group consisting of alkylgroups having 1 to 30 carbon atoms, alicyclic groups, aryl groups,aralkyl groups, and fluorinated alkyl groups, m and n may be the samewith and different from each other and are integers of from 0 to 300,and s and t may be the same with or different from each other and areintegers of from 0 to 3 with 1≦n+s+t.
 11. The hair cosmetic according toclaim 6 wherein the hair cosmetic further comprises one or more of anunctuous agent (B).
 12. The hair cosmetic according to claim 11, whereinat least part of the unctuous agent (B) is selected from the groupconsisting of organopolysiloxanes having a viscosity of from 0.65 to1,000,000 mm²/s, cyclic siloxanes, and silicone rubbers or resinsdissolved or dispersed in a cyclic siloxane.
 13. The hair cosmeticaccording to claim 11 or 12, wherein at least part the aforesaidunctuous agent (B) has a fluorine-containing group.
 14. The haircosmetic according to claim 6, wherein the hair cosmetic furthercomprises water (C).
 15. The hair cosmetic according to claim 6, whereinthe hair cosmetic further comprises a compound (D) having an alcoholichydroxyl group in a molecule.
 16. The hair cosmetic according to claim6, wherein the hair cosmetic further comprises a water-soluble orwater-swelling polymer (E).
 17. The hair cosmetic according to claim 6,wherein the hair cosmetic further comprises a surfactant (F).
 18. Thehair cosmetic according to claim 17, wherein the surfactant (F) is alinear or branched polyoxyalkylene-modified organopolysiloxane.
 19. Thehair cosmetic according to claim 17, wherein the surfactant (F) is alinear or branched polyglycerin-modified organopolysiloxane.
 20. Thehair cosmetic according to claim 6, wherein the hair cosmetic furthercomprises a crosslinked organopolysiloxane (G).
 21. The hair cosmeticaccording to claim 20, wherein the crosslinked organopolysiloxane (G)has been incorporated in the cosmetic in a state swollen in a siliconehaving a viscosity of from 0.65 to 10.0 mm²/sec in an amount larger thana weight of the crosslinked organopolysiloxane (G).
 22. The haircosmetic according to claim 20 or 21, wherein the crosslinkedorganopolysiloxane (G) is a reaction product of an organopolysiloxanehaving at least two alkenyl groups per molecule with anorganohydrogenpolysiloxane having a Si—H bond.
 23. The hair cosmeticaccording to claim 20, wherein the crosslinked organopolysiloxane (G)has at least one moiety selected from the group consisting ofpolyoxyalkylene moieties, polyglycerin moieties, alkyl moieties, alkenylmoieties, aryl moieties and fluoroalkyl moieties.
 24. The hair cosmeticaccording to claim 6, wherein the cosmetic further comprises a siliconeresin (H) selected from the group consisting of acrylsilicone resinswhich do not have a hydrolyzable silyl group, silicone network compoundsrepresented as MQ, MDQ, MT, MDT, or MDTQ, and silicone network compoundshaving at least one moiety selected from the group consisting ofpyrrolidone moieties, long-chain alkyl moieties, polyoxyalkylenemoieties, fluoroalkyl moieties, and amino moieties.
 25. The haircosmetic according to claim 6, wherein the cosmetic further comprisesone or more of powder and/or coloring agent (I).
 26. The hair cosmeticaccording to claim 25, wherein at least part of the powder and/orcoloring agent (I) is crosslinked silicone fine powder with a structureof crosslinked dimethylsilicone, polymethylsilsesquioxane fine powder,silica made hydrophobic, or composite fine powder composed of sphericalsilicone rubber coated with polymethylsilsesquioxane particles.
 27. Thehair cosmetic according to claim 6, wherein the cosmetic is in the formof liquid, milky lotion, cream, solid, paste, gel, multilayer, mousse,spray or stick.
 28. A method to prepare the hair treatment agentaccording to claim 1, wherein the method comprises: the step ofcopolymerizing 1 to 97 wt % of an organopolysiloxane represented by thefollowing formula (4) having a radically polymerizable group, 0 to 95 wt% of an acrylic monomer represented by the following formula (5), and 1to 10 wt % of a silane compound represented by the following formula (6)having a radically polymerizable group,

wherein R¹, R² and R³ may be the same with or different from each otherand are selected from the group consisting of alkyl groups having 1 to30 carbon atoms, aryl groups, aralkyl groups and fluorinated alkylgroups, A is a radically polymerizable group represented by thefollowing formula (7),CH₂═C(R⁴)R⁵—  (7), wherein R⁴ is a hydrogen atom or a methyl group andR⁵ is an alkyleneoxycarbonyl group having 2 to 11 carbon atoms or aphenylene group, and n is an integer of from 3 to 500;CH₂═C(R⁶)COOR⁷  (5), wherein R⁶ is a hydrogen atom or a methyl group andR⁷ is an alkyl group having 1 to 30 carbon atoms;B—Si(CH₃)_(3-m)(OR⁸)_(m)  (6), wherein B is selected from the groupsdefined for A above, independently of A, R⁸ is an alkyl group having 1to 4 carbon atoms or an alkenyl group, m is an integer of from 1 to 3,and R⁸'s may be different from each other when m is 2 or 3.